Agglutinant for Pellicle, Pellicle, Exposure Original Plate with Pellicle, Method for Producing Semiconductor Device, Method for Producing Liquid Crystal Display Board, Method for Regenerating Exposure Original Plate, and Peeling Residue Reduction Method

ABSTRACT

Provided is an agglutinant for pellicles that can reduce residues stuck onto an exposure original plate when a pellicle is peeled from the exposure original plate after being used in lithography, in particular ArF lithography, and also provided are a pellicle, an exposure original plate with a pellicle, a method for regenerating an exposure original plate, and a peeling residue reduction method.An agglutinant for pellicles for bonding a pellicle to an exposure original plate, in which the agglutinant includes an acrylic polymer having an SP value of 10.0 or more and 12.0 or less as a base material.

FIELD OF THE INVENTION

The present invention relates to an agglutinant for pellicles, apellicle, an exposure original plate with a pellicle, a method forproducing a semiconductor device, a method for producing a liquidcrystal display board, a method for regenerating an exposure originalplate, and a peeling residue reduction method.

TECHNICAL BACKGROUND OF THE INVENTION

In manufacturing semiconductor devices such as LSI and super-LSI or inmanufacturing a liquid crystal display board or the like, a pattern ismade by irradiating light to a semiconductor wafer or an original platefor liquid crystal, but if dust is attached to an exposure originalplate used in this case, the dust absorbs the light or bends the light.As a result, the transferred pattern would be deformed, and theresulting pattern would have roughened edges or black stains on thebase, which would lead to problems such as damaged dimensions, poorquality, and deformed external appearance. In the present invention, the“exposure original plate” is a generic name of lithography masks andreticles.

These works are usually performed in a cleanroom, but it is difficult tokeep the exposure original plate clean all the time even in thecleanroom. Therefore, a pellicle that transmits light for exposure wellis bonded to a surface of the exposure original plate as a dust-fender.

Under such circumstances, the dust does not directly adhere to thesurface of the exposure original plate but adhere only to the pelliclefilm. Accordingly, when the focus is set on the pattern of the exposureoriginal plate during lithography, the dust on the pellicle film becomesirrelevant to transfer.

The basic structure of the pellicle comprises a pellicle frame and apellicle film stretched over the pellicle frame. The pellicle film ismade of nitrocellulose, cellulose acetate, a fluorine-based polymer, orthe like that well transmits light used for exposure (g-rays, i-rays,248 nm, 193 nm, 157 nm, etc.). The pellicle frame is made of an aluminumalloy such as A7075, A6061, or A5052 treated with black alumite or thelike, stainless steel, polyethylene, or the like. A good solvent of apellicle film is applied to the upper part of the pellicle frame, andthe pellicle film is bonded by air-drying or using an adhesive materialsuch as an acrylic resin, an epoxy resin, or fluororesin. Further, sincethe lower part of the pellicle frame is mounted with an exposureoriginal plate, an agglutinant layer obtained from a polybutene resin, apolyvinyl acetate resin, an acrylic resin, a silicone resin, or thelike, and a protective liner for protecting the agglutinant layer areprovided.

The pellicle is provided so as to surround a pattern region formed onthe surface of the exposure original plate. Since the pellicle isprovided to prevent the adhesion of dust to the exposure original plate,the pattern region and the outside of the pellicle are isolated fromeach other so that dust from the outside of the pellicle does not adhereto the pattern surface.

In recent years, miniaturization of LSI design rules to sub-quartermicrons has progressed. Along with this, the wavelength of exposurelight sources is becoming shorter. That is, the trend is moving fromg-rays (436 nm) and i-rays (365 nm) produced by mercury lamps, whichhave been the mainstream until now, to KrF excimer laser (248 nm), ArFexcimer laser (193 nm), F₂ laser (157 nm), and the like. As a result ofprogress in miniaturization, the allowable size of foreign substancesand haze that may be generated on the pattern face of the mask substrateto which the pellicle is bonded is becoming more and more strict.

PRIOR ART PUBLICATIONS Publications

-   IP Publication 1: Japanese Patent No. 5638693-   IP Publication 2: Japanese Patent Application Publication No.    2016-18008-   IP Publication 3: Japanese Patent Application Publication No.    2006-146085-   IP Publication 4: Japanese Patent Application Publication No.    2008-21182

SUMMARY OF THE INVENTION Problems the Invention Seeks to Solve

In recent years, phase shift films have been commonly used as masksubstrate films to meet the miniaturization of design rules. However,phase shift films are very delicate, and mask cleaning under excessiveconditions may cause damage, such as corrosion and scraping, to thephase shift films. For this reason, in recent years, there has been atendency to reconsider chemicals used for mask cleaning, and to weakenthe cleaning conditions.

Furthermore, the mask pattern of advanced mask products is shifting frompositive type mask patterns, which have been the mainstream until now,to negative type mask patterns. As a result, there are many situationswhere no light-shading layer is provided in the portion to which thepellicle is bonded. If there is no light-shading layer, there is apossibility that the pellicle agglutinant is irradiated with an exposurelight beam through the mask substrate. In that case, more residues ofthe agglutinant layer may remain on the mask substrate when the pellicleis peeled.

During use of a pellicle bonded to a mask, if foreign substances andhaze are generated, or if the pellicle film is damaged, it is necessaryto peel the pellicle, subject the mask to regeneration cleaning, andbond a new pellicle (which is hereinafter referred to as “repellicle”).It is the most important for repellicle that regeneration cleaning isperformed so that the mask is kept in a state of high cleanliness;however, in order to carry out regeneration cleaning of the mask underrecent weak cleaning conditions, it is important to reduce residuesremaining on the mask substrate when the pellicle is peeled.

As regeneration cleaning, cleaning with chemicals such as sulfuric acidhydrogen peroxide or ammonia hydrogen peroxide, and physical cleaning bybrushes, sponges, or the like are generally used. However, regenerationcleaning with functional water is being studied to prevent damage tophoto masks and sulfate ions from remaining on the photo masks.

Functional water is generally defined by the Japanese Society forFunctional Water as, among aqueous solutions that have been givenreproducible and useful functions by artificial treatment, those forwhich the scientific basis for treatment and function has beenclarified, and those for which such scientific basis is about to beclarified. Specific examples thereof include fine bubble water such asozone water, hydrogen water, micro-bubble water, and nano-bubble water;electrolyzed water, supercritical water, subcritical water, and thelike. Ozone water and hydrogen water are often used to clean photomasks. In addition, the cleaning power can be improved by adding a smallamount of ammonia.

However, the present inventors found that since the cleaning power offunctional water was weaker than that of chemicals such as sulfuric acidhydrogen peroxide, in the regeneration cleaning of the photo mask afterthe removal of the pellicle, residues of the agglutinant layer thatfixed the pellicle and the photo mask were difficult to remove only byfunctional water cleaning. In particular, in phase shift photo masks,damage to phase shift films leads to changes in transmittance and phasedifference, and it is thus difficult to add physical cleaning inaddition to functional water cleaning.

Moreover, when lithography is performed using an exposure light beamsuch as ArF excimer laser (193 nm) on a lithography pellicle in which apellicle film is stretched over the upper end face of a pellicle framethrough a pellicle film bonding adhesive material layer, and in which amask bonding agglutinant layer is provided on the other end face, thereis a problem that the agglutinant layer formed on the lower end face ofthe pellicle frame is altered by the exposure light beam, and manyaltered parts of the agglutinant layer remain on the exposure originalplate as peeling residues when peeling from the exposure original plate.

Attempts have been made so far to reduce residues by adding surfacemodifiers or the like to agglutinants (IP Publications 1 and 2 describedabove). Further, as techniques of reducing residues, a large pelliclehaving an agglutinant layer with a cohesive fracture strength of 20g/mm² or more (IP Publication 3 described above), and a pelliclecomprising an agglutinant for pellicles and having a ratio of peelingstrength and tensile strength of 0.10 or more and 0.33 or less aredisclosed (IP Publication 4 described above).

The present invention was made in view of such circumstances, and anobject of the present invention is to provide an agglutinant forpellicles that can reduce residues stuck onto an exposure original platewhen a pellicle is peeled from the exposure original plate after beingused in lithography, in particular ArF lithography, and to also providea pellicle, an exposure original plate with a pellicle, a method forregenerating an exposure original plate, and a peeling residue reductionmethod. Another object of the present invention is to provide a methodfor producing a semiconductor device and a method for producing a liquidcrystal display board that can thereby improve production efficiency.

Means to Solve the Problems

[1] An agglutinant for pellicles for bonding a pellicle to an exposureoriginal plate, the agglutinant comprising an acrylic polymer having anSP value of 10.0 or more and 12.0 or less as a base material.

[2] An agglutinant for pellicles for bonding a pellicle to an exposureoriginal plate, the agglutinant comprising an acrylic polymer as a basematerial, the acrylic polymer comprising a (meth)acrylic acid esterhaving an ether bond as a monomer component.

[3] An agglutinant for pellicles as claimed in [2] described above,wherein the (meth)acrylic acid ester having an ether bond is a(meth)acrylic acid ester having an alkylene oxide group.

[4] An agglutinant for pellicles as claimed in [3] described above,wherein the (meth)acrylic acid ester having an ether bond is containedin an amount of 30 mass % or more based on the whole monomer components.

[5] An agglutinant for pellicles as claimed in [3] or [4] describedabove, wherein the alkylene oxide group is an ethylene oxide group.

[6] An agglutinant for pellicles as claimed in any one of [2] to [5]described above, further comprising an unsaturated monomer having acarboxyl group or a hydroxyl group as a monomer component.

[7] An agglutinant for pellicles as claimed in any one of [2] to [6]described above, further comprising a (meth)acrylic acid alkyl ester asa monomer component.

[8] An agglutinant for pellicles for bonding a pellicle to an exposureoriginal plate, the agglutinant comprising an acrylic polymer as a basematerial, the acrylic polymer having a side chain containing an etherbond.

[9] An agglutinant for pellicles as claimed in [8] described above,wherein the side chain containing an ether bond has an alkylene oxidegroup.

[10] An agglutinant for pellicles as claimed in [9] described above,wherein the alkylene oxide group is an ethylene oxide group.

[11] An agglutinant for pellicles for bonding a pellicle to an exposureoriginal plate, the agglutinant comprising an acrylic polymer as a basematerial, the acrylic polymer having a side chain that has higherdegradability by irradiation with an exposure light beam than a mainchain.

[12] An agglutinant for pellicles for bonding a pellicle to an exposureoriginal plate, the agglutinant comprising an acrylic polymer as a basematerial, the acrylic polymer having a side chain that is selectivelydegraded by irradiation with an exposure light beam.

[13] A pellicle frame with an agglutinant layer, comprising a pellicleframe and an agglutinant layer provided on one end face of the pellicleframe and obtained from an agglutinant for pellicles as claimed in anyone of [1] to [12] described above.

[14] A pellicle comprising a pellicle film, a pellicle frame providedwith the pellicle film on one end face thereof, and an agglutinant layerprovided on the other end face of the pellicle frame and obtained froman agglutinant for pellicles as claimed in any one of [1] to [12]described above.

[15] A pellicle as claimed in [14] described above, wherein theagglutinant layer is irradiated with an exposure light beam.

[16] A pellicle as claimed in [14] described above, wherein the pellicleis bonded to a phase shift photo mask.

[17] A pellicle as claimed in [14] described above, wherein the pellicleis bonded to a negative type exposure original plate.

[18] A pellicle as claimed in [14] described above, wherein the pellicleis bonded to an exposure original plate that has a non-shaded area or asemi-transparent shaded area in a portion thereof to which anagglutinant layer is bonded.

[19] A pellicle as claimed in [14] described above, wherein the pellicleis bonded to an exposure original plate that has a transparent area in aportion thereof to which an agglutinant layer is bonded.

[20] A pellicle as claimed in [14] described above, wherein the pellicleis bonded to a face comprising silicon oxide as a main component.

[21] A pellicle as claimed in [20] described above, wherein the facecomprising silicon oxide as a main component is a quartz face.

[22] A pellicle as claimed in [14] described above, wherein the pellicleis compatible with regeneration cleaning with functional water.

[23] An exposure original plate with a pellicle, comprising an exposureoriginal plate and a pellicle as claimed in [14] or [15] described abovemounted on the exposure original plate.

[24] An exposure original plate with a pellicle as claimed in [23]described above, wherein the exposure original plate is a phase shiftphoto mask.

[25] An exposure original plate with a pellicle as claimed in [23]described above, wherein the exposure original plate is of negativetype.

[26] An exposure original plate with a pellicle as claimed in [23]described above, wherein a portion of the exposure original plate towhich the agglutinant layer is bonded has a non-shaded area or asemi-transparent shaded area.

[27] An exposure original plate with a pellicle as claimed in [23]described above, wherein a portion of the exposure original plate towhich the agglutinant layer is bonded has a transparent area.

[28] An exposure original plate with a pellicle as claimed in [23]described above, wherein the exposure original plate comprises siliconoxide as a main component.

[29] An exposure original plate with a pellicle as claimed in [23]described above, wherein the exposure original plate is a quartzsubstrate.

[30] A method for producing a semiconductor device, comprising a step ofperforming exposure using an exposure original plate with a pellicle asclaimed in any one of [23] to [29] described above.

[31] A method for producing a liquid crystal display board, comprising astep of performing exposure using an exposure original plate with apellicle as claimed in any one of [23] to [29] described above.

[32] A method for regenerating an exposure original plate, comprisingpeeling a pellicle from an exposure original plate with a pellicle asclaimed in any one of [23] to [29] described above, and cleaningresidues of an agglutinant remaining on the exposure original plate withfunctional water to regenerate the exposure original plate.

[33] A peeling residue reduction method comprising, when peeling apellicle from an exposure original plate to which the pellicle isbonded, reducing peeling residues of an agglutinant layer of thepellicle remaining on the exposure original plate, wherein the methoduses a pellicle as claimed in any one of [14] to [22] described above asthe pellicle.

[34] An application of a pellicle comprising a pellicle film, a pellicleframe provided with the pellicle film on one end face thereof, and anagglutinant layer provided on the other end face of the pellicle frameand obtained from an agglutinant for the pellicle, wherein theagglutinant layer is irradiated with an exposure light beam.

[35] An application of a pellicle comprising a pellicle film, a pellicleframe provided with the pellicle film on one end face thereof, and anagglutinant layer provided on the other end face of the pellicle frameand obtained from an agglutinant for the pellicle, wherein the pellicleis bonded to a phase shift photo mask.

[36] An application of a pellicle comprising a pellicle film, a pellicleframe provided with the pellicle film on one end face thereof, and anagglutinant layer provided on the other end face of the pellicle frameand obtained from an agglutinant for the pellicle, wherein the pellicleis bonded to a negative type exposure original plate.

[37] An application of a pellicle comprising a pellicle film, a pellicleframe provided with the pellicle film on one end face thereof, and anagglutinant layer provided on the other end face of the pellicle frameand obtained from an agglutinant for the pellicle, wherein the pellicleis bonded to an exposure original plate that has a non-shaded area or asemi-transparent shaded area in a portion thereof to which theagglutinant layer is bonded.

[38] An application of a pellicle comprising a pellicle film, a pellicleframe provided with the pellicle film on one end face thereof, and anagglutinant layer provided on the other end face of the pellicle frameand obtained from an agglutinant for the pellicle, wherein the pellicleis bonded to an exposure original plate that has a transparent area in aportion thereof to which the agglutinant layer is bonded.

[39] An application of a pellicle comprising a pellicle film, a pellicleframe provided with the pellicle film on one end face thereof, and anagglutinant layer provided on the other end face of the pellicle frameand obtained from an agglutinant for the pellicle, wherein the pellicleis bonded to a face comprising silicon oxide as a main component (inparticular, a quartz face).

[40] An application of a pellicle comprising a pellicle film, a pellicleframe provided with the pellicle film on one end face thereof, and anagglutinant layer provided on the other end face of the pellicle frameand obtained from an agglutinant for the pellicle, wherein the pellicleis compatible with regeneration cleaning with functional water.

[41] A peeling residue reduction pellicle comprising a pellicle film, apellicle frame provided with the pellicle film bonded to one end facethereof, and an agglutinant layer for bonding the pellicle provided onthe other end face of the pellicle frame to an exposure original plate,wherein the agglutinant layer comprises an acrylic resin having an SPvalue of 10.0 or more and 12.0 or less as a base material.

[42] A peeling residue reduction pellicle as claimed in [41] describedabove, wherein the agglutinant layer further contains a polyvinyl ethercompound.

[43] A peeling residue reduction pellicle as claimed in [41] or [42]described above, wherein the peeling residue reduction pellicle is apeeling residue reduction pellicle for ArF lithography.

[44] A method for producing a peeling residue reduction pellicle, themethod comprising selecting an agglutinant for bonding the pellicle toan exposure original plate, applying the agglutinant to one end face ofa pellicle frame to form an agglutinant layer, peelably bonding aprotective member thereto, applying an adhesive material to the otherend face of the pellicle frame, and bonding a pellicle film thereto,wherein in selection of the agglutinant, one comprising an acrylic resinhaving an SP value of 10.0 or more and 12.0 or less as a base materialis selected.

[45] A method for producing a peeling residue reduction pellicle asclaimed in [44] described above, wherein the agglutinant layer furthercontains a polyvinyl ether compound.

[46] A method for reducing, when a pellicle is peeled from an exposureoriginal plate to which the pellicle is bonded, peeling residues of anagglutinant layer of the pellicle remaining on the exposure originalplate, wherein the method uses a pellicle as claimed in any one of [41]to [43] described above as the pellicle.

Effects of the Invention

The present invention can provide a pellicle that can reduce peelingresidues stuck onto an exposure original plate when a pellicle is peeledfrom the exposure original plate after being used in lithography, inparticular ArF lithography, and can also provide an exposure originalplate with a pellicle, a method for regenerating an exposure originalplate, and a peeling residue reduction method. According to thepellicle, exposure original plate with a pellicle, method forregenerating an exposure original plate, and peeling residue reductionmethod of the present invention, even when an exposure light beam isapplied through the exposure original plate, the pellicle can be peeledfrom the exposure original plate with very few peeling residues of theagglutinant. As a result, the regeneration cleaning of the exposureoriginal plate, from which the pellicle is removed, can proceedsmoothly, and the cleaning conditions can be loosened; thus, there is anadvantage in reducing damage to the exposure original plate surfaceduring cleaning. In addition, production efficiency can be improved inthe production of semiconductor devices and liquid crystal displayboards.

In the pellicle of the present invention, it is assumed that since aspecific acrylic polymer (also referred to as an acrylic resin) is usedas the base material of the agglutinant, the intermolecular force insidethe agglutinant is improved, appropriate adhesive strength can bemaintained, and not only large residues but also particulate residuesare reduced during peeling from the exposure original plate.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 A conceptual diagram showing the basic structure of the pellicleof the present invention.

EXAMPLES TO EMBODY THE INVENTION

First, the basic structure of the pellicle of the present invention willbe described with reference to FIG. 1.

As shown in FIG. 1, the pellicle 10 of the present invention is suchthat a pellicle film 12 is stretched over the upper end face of apellicle frame 11 through an adhesive material layer 13 for bonding thepellicle film. In this case, an agglutinant layer 14 for bonding thepellicle 10 to an exposure original plate (mask substrate or reticle) 1is generally formed on the lower end face of the pellicle frame 11, anda liner (not shown) is peelably bonded to the lower end face of theagglutinant layer 14. In addition, the pellicle frame 11 may be providedwith an air pressure adjustment hole (vent) 15, and may be furtherprovided with a dust removal filter 16 for the purpose of removingparticles.

In this case, the size of these pellicle constituent members isequivalent to that of general pellicles, for example, pellicles forsemiconductor lithography and pellicles for the lithography step in theproduction of large liquid crystal display boards. Moreover, thematerials thereof can be known materials as described above.

The type of pellicle film 12 is not particularly limited. For example,amorphous fluoropolymers conventionally used for excimer laser are used.Examples of amorphous fluoropolymers include Cytop (trade name of AGCInc.), Teflon (registered trademark) AF (trade name of DuPont), and thelike. These polymers may be used after being dissolved in solvents, ifnecessary, during the production of pellicle films, and can be suitablydissolved, for example, in fluorine type solvents.

As for the base material of the pellicle frame 11, for example, aluminumalloy materials, preferably JIS A7075, JIS A6061, and JIS A5052materials, are used. When an aluminum alloy material is used, there isno particular limitation as long as the strength as the pellicle frameis ensured. The pellicle frame surface is preferably roughened bysandblasting or chemical polishing, and a polymer coating may beprovided after roughening. In the present invention, a conventionallyknown method can be employed as the method for roughening the framesurface. In a preferable method, the surface of an aluminum alloymaterial is subjected to blast treatment using stainless steel,carborundum, glass beads, or the like, and is further subjected tochemical polishing using NaOH or the like, thereby roughening thesurface.

By the way, the present inventors conducted many discussions andexperiments in order to solve the above problems of the presentinvention, particularly focused on the feature of the agglutinantforming the agglutinant layer, and comparatively analyzed theexperimental results. As a result, the present inventors found that thefollowing means was effective.

That is, a first aspect of the agglutinant for pellicles of the presentinvention is to use an acrylic polymer having an SP value of 10.0 ormore and 12.0 or less as a base material. Due to the acrylic polymerhaving an SP value of 10.0 or more and 12.0 or less, when the pellicleis peeled from the exposure original plate, peeling residues of theagglutinant layer remaining on the exposure original plate can bereduced. When the SP value is 10.0 or more, residues that can hardly beremoved by cleaning can be reduced. On the other hand, when the SP valueis 12.0 or less, the volatility of the agglutinant can be reduced, whichleads to the suppression of haze. The present inventors assume that theeffects of the present invention can be obtained by improving thehydrophilicity of the acrylic polymer by setting the SP value within thespecific range.

A second aspect of the agglutinant for pellicles of the presentinvention is to use, as a base material, an acrylic polymer comprising a(meth)acrylic acid ester having an ether bond as a monomer component.Because a (meth)acrylic acid ester having an ether bond is contained asa monomer component of an acrylic polymer, when the pellicle is peeledfrom the exposure original plate, peeling residues of the agglutinantlayer remaining on the exposure original plate can be reduced. Due tothe introduction of an ether bond into an acrylic polymer, it becomeseasy to control the hydrophilicity of the acrylic polymer. In addition,due to the introduction of an ether bond into the side chain of anacrylic polymer, the ether bond is assumed to preventlight-deterioration of the main chain.

A third aspect of the agglutinant for pellicles of the present inventionis to use, as a base material, an acrylic polymer having a side chaincontaining an ether bond. Because an ether bond is contained in the sidechain of an acrylic polymer, when the pellicle is peeled from theexposure original plate, peeling residues of the agglutinant layerremaining on the exposure original plate can be reduced. Due to theintroduction of an ether bond into an acrylic polymer, it becomes easyto control the hydrophilicity of the acrylic polymer. In addition, theintroduction of an ether bond into the side chain of an acrylic polymeris assumed to prevent light-deterioration of the main chain.

A fourth aspect of the agglutinant for pellicles of the presentinvention is to use, as a base material, an acrylic polymer having aside chain that has higher degradability by irradiation with an exposurelight beam than a main chain. Because the degradability of the sidechain of the acrylic polymer by irradiation with an exposure light beamis higher than that of the main chain, when the pellicle is peeled fromthe exposure original plate, peeling residues of the agglutinant layerremaining on the exposure original plate can be reduced. It is assumedthat since the degradability of the side chain by the exposure lightbeam is higher than that of the main chain, the degradation of the sidechain substantially precedes the degradation of the main chain, andpeeling residues can be reduced. The degradation of the side chain hasless effect on the deterioration of the agglutinant, and even if thedegradation proceeds, it is considered that the agglutinant is lesslikely to remain as peeling residues during peeling due to the cohesiveforce of the agglutinant. On the other hand, if the light-deteriorationof the main chain proceeds, the molecular weight of the main chain isreduced, and it is considered that the reduced-molecular-weightagglutinant remains on the substrate as residues. Here, the differencein degradability can be determined, for example, by comparing thedecomposition product of the main chain and the decomposition product ofthe side chain before and after irradiation of the agglutinant with anexposure light beam by IR, NMR, or the like. More specifically, it canbe confirmed by comparing the IR chart of the agglutinant beforeirradiation with an exposure light beam with the IR chart of theagglutinant after irradiation with an exposure light beam, and observingthe change in spectral intensity. Examples of the wave number to beconfirmed include C—O—C (methoxy group) at 1125 cm⁻¹, C—O—C (ethergroup) at 1160 cm⁻¹, C═O (ester group) at 1727 cm⁻¹, and the like.

A fifth aspect of the agglutinant for pellicles of the present inventionis to use, as a base material, an acrylic polymer having a side chainthat is selectively deteriorated by irradiation with an exposure lightbeam. Because the side chain of the acrylic polymer is selectivelydeteriorated by irradiation with an exposure light beam, when thepellicle is peeled from the exposure original plate, peeling residues ofthe agglutinant layer remaining on the exposure original plate can bereduced. It is assumed that since the side chain is selectivelydeteriorated by irradiation with an exposure light beam, the degradationof the side chain substantially precedes the degradation of the mainchain, and peeling residues can be reduced. The degradation of the sidechain has relatively less effect on the deterioration of theagglutinant, and even if the degradation proceeds, it is considered thatthe agglutinant is less likely to remain as peeling residues duringpeeling due to the cohesive force of the agglutinant. On the other hand,if the light-deterioration of the main chain proceeds, the molecularweight of the main chain is reduced, and it is considered that thereduced-molecular-weight agglutinant remains on the substrate asresidues. Here, the presence of deterioration can be determined, forexample, by comparing the decomposition product of the main chain andthe decomposition product of the side chain before and after irradiationof the agglutinant with an exposure light beam by IR, NMR, or the like.More specifically, it can be confirmed by comparing the IR chart of theagglutinant before irradiation with an exposure light beam with the IRchart of the agglutinant after irradiation with an exposure light beam,and observing the change in spectral intensity. Examples of the wavenumber to be confirmed include C—O—C (methoxy group) at 1125 cm⁻¹, C—O—C(ether group) at 1160 cm⁻¹, C═O (ester group) at 1727 cm⁻¹, and thelike.

In the present invention, the “agglutinant comprising an acrylic polymeras a base material” refers to an agglutinant containing an acrylicpolymer itself or an agglutinant containing a reaction product of theacrylic polymer, a curing agent, and the like.

The present inventors found that in a pellicle provided with anagglutinant layer obtained from such an agglutinant, the agglutinantlayer suppressed deterioration due to an exposure light beam, and thateven if deterioration occurred, peeling residues were less likely to begenerated during peeling from the mask substrate (exposure originalplate).

In the present invention, the acrylic polymer mentioned above is, forexample, a polymer comprising a (meth)acrylic acid ester as a monomercomponent, and a monomer component copolymerizable with the(meth)acrylic acid ester can be copolymerized, if necessary. Examples ofthe (meth)acrylic acid ester include (meth)acrylic acid esters having anether bond, (meth)acrylic acid alkyl esters, unsaturated monomers havinga carboxyl group or a hydroxyl group, and the like. When a (meth)acrylicacid ester having an ether bond is contained as a monomer component, theether bond can be introduced into the side chain of the acrylic polymer.

Examples of the (meth)acrylic acid ester having an ether bond ((A)component) include (meth)acrylic acid esters having an alkylene oxidegroup, such as an ethylene oxide group, a propylene oxide group, or abutylene oxide group. Among these, (meth)acrylic acid esters having anethylene oxide group (also referred to as ethylene oxidegroup-containing (meth)acrylates) are preferable. Examples thereofinclude methoxypolyethylene glycol (meth)acrylates, such as2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate,2-butoxyethyl (meth)acrylate, phenoxyethylene glycol (meth)acrylate, andmethoxydiethylene glycol (meth)acrylate; ethoxypolyethylene glycol(meth)acrylates, such as ethoxydiethylene glycol (meth)acrylate;butoxypolyethylene glycol (meth)acrylates, such as butoxydiethyleneglycol (meth)acrylate; phenoxypolyethylene glycol (meth)acrylates, suchas phenoxydiethylene glycol (meth)acrylate; and the like. These may beused singly or in combination of two or more.

Examples of the (meth)acrylic acid alkyl ester ((B) component) include(meth)acrylic acid alkyl esters having a C₁₋₁₄ alkyl group, and thelike. Specific examples thereof include methyl (meth)acrylate, ethyl(meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl(meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate,2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl(meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, and thelike. Among these, (meth)acrylic acid alkyl esters having a C₄ or C₈alkyl group are preferable, in terms of satisfying both agglutinantcharacteristics and peeling characteristics. These may be used singly orin combination of two or more.

Examples of the unsaturated monomer having a carboxyl group or ahydroxyl group ((C) component) include α,β-unsaturated carboxylic acids,such as (meth)acrylic acid, maleic acid, crotonic acid, itaconic acid,and fumaric acid; hydroxyl group-containing methacrylates, such as2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and2-hydroxybutyl (meth)acrylate; and the like. These may be used singly orin combination of two or more.

The ratio of the (A) component used in the acrylic polymer is preferably30 mass % or more, more preferably 35 mass % or more, particularlypreferably 35 to 98 mass %, and extremely preferably 40 to 95 mass %, inthe whole monomer components. Because of the ratio of the (A) componentwithin the above range, it becomes easy to control peeling residues andlight resistance.

The ratio of the (B) component used in the acrylic polymer is preferably0 to 70 mass %, and more preferably 3 to 55 mass %, in the whole monomercomponents. Because of the ratio of the (B) component within the aboverange, it becomes easy to control adhesion.

The ratio of the (C) component used in the acrylic polymer is preferably0 to 10 mass %, and more preferably 2 to 8 mass % in the whole monomercomponents. Because of the ratio of the (C) component within the aboverange, it becomes easy to control peeling residues and the degree ofcrosslinking due to the reaction with a curing agent.

The acrylic polymer can be produced, for example, by selecting a knownproduction method, such as solution polymerization, bulk polymerization,emulsion polymerization, or radical polymerization. Further, theobtained acrylic polymer may be any of a random copolymer, a blockcopolymer, a graft copolymer, and the like.

When the molecular weight of the acrylic polymer is within the range of700,000 to 2.5 million as weight average molecular weight, theagglutinant layer has moderate cohesive force and adhesive strength, andthe agglutinant causes less adhesive residues and has sufficientadhesive strength and load resistance, which is preferable.

The weight average molecular weight mentioned above is a value measuredby gel permeation chromatography (GPC) analysis, and refers to a valuein terms of standard polystyrene. The GPC analysis can be performedusing tetrahydrofuran (THF) as an eluent.

In the present embodiment, a reaction product of the acrylic polymer anda curing agent is preferably contained as the agglutinant of theagglutinant layer; however, in terms of flexibility, an acrylic polymerthat does not react with the curing agent may be contained.

The curing agent is not particularly limited as long as it is a curingagent that is used as a general agglutinant, and examples thereofinclude metal salts, metal alkoxides, aldehyde type compounds, non-aminoresin type amino compounds, urea type compounds, isocyanate typecompounds, polyfunctional epoxy compounds, metal chelate type compounds,melamine type compounds, aziridine type compounds, and the like. Amongthese, isocyanate type compounds and epoxy compounds are preferable, interms of the reactivity with the carboxyl group or the hydroxyl group.

Examples of isocyanate type compounds include xylylene diisocyanate,hexamethylene diisocyanate, tolylene diisocyanate, and multimers,derivatives, and polymers thereof, and the like. These may be usedsingly or in combination of two or more.

Examples of epoxy compounds include compounds having two or more epoxygroups in the molecule, and specific examples thereof include ethyleneglycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerindiglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidylether, trimethylolpropane triglycidyl ether, diglycidylaniline, diamineglycidylamine, N,N,N′,N′-tetraglycidyl-m-xylylenediamine,1,3-bis(N,N′-diamineglycidylaminomethyl), and the like. These may beused singly or in combination of two or more.

In the present invention, the definition of the SP value is as describedbelow.

[Method for Calculating SP Value]

In the present invention, the SP value is a solubility parameter. The SPvalue can be determined by the following Equation 1 with reference tothe Fedors calculation method [“Polymer Engineering and Science,” Vol.14, No. 2 (1974), pp. 148-154].

$\begin{matrix}{\delta = \left( \frac{\sum\limits_{i}{\Delta ei}}{\sum\limits_{i}{\Delta vi}} \right)^{\frac{1}{2}}} & \left\lbrack {{Equation}\mspace{14mu} 1} \right\rbrack\end{matrix}$

In the above Equation 1, δ is a solubility parameter (SP value), Δei ismolar evaporation energy, and Δvi is molar volume. Further, the unit ofthe solubility parameter is (cal/mol)^(1/2). Table 1 shows theeigenvalues of Δei and Δvi given to the main atoms or atomic groups withrespect to the above Equation 1.

TABLE 1 Atom or atomic group

 ei (cal/mol)

 vi (cm³/mol) C 350 −19.2 —CH₂— 1180 16.1 —CH₃ 1125 33.5 CH₂═ 1030 28.5—CH═ 1030 13.5 -phenyl 7630 71.4 —O— 800 3.8 —CO— 4150 10.8 —COO— 430018.0 —OH 7120 10.0 —CONH₂ 10000 17.5 —CONH— 8000 9.5 —NH₂ 3000 19.2 —NH—2000 4.5 —CN 6100 24.0 —COOH 6600 28.5 Si 810 0.0 F 1000 18.0 Cl 276024.0

The SP value (solubility parameter) of the acrylic polymer is preferably10.0 to 12.0, and more preferably 10.0 to 11.0.

The SP value of the acrylic polymer can be controlled, for example, bychanging the concentration of polar groups in the acrylic polymer. Forexample, when a relatively higher polar bond, such as an ether bond, isintroduced into the side chain, the SP value tends to increase. On theother hand, when a relatively less polar bond, such as a long-chainalkylene bond, is introduced into the side chain, the SP value tends todecrease.

In the agglutinant of the present invention, two or more acrylicpolymers, such as two or more acrylic polymers having different weightaverage molecular weights, two or more acrylic polymers containingdifferent monomer components, or two or more acrylic polymers withdifferent copolymerization ratios, may be combined as the base material.In such case, within the range in which the effects of the presentinvention are exhibited, the SP value of only a single acrylic polymermay be within the range, or the SP values of all of the acrylic polymersmay be out of the range, but the SP value of the entire acrylic polymercomponent may be within the range. Here, the SP value of the entireacrylic polymer component is calculated by dividing the SP value of eachof two or more acrylic polymers proportionally by their respectivemixing amounts.

In order to reduce distortion and other influences on the mask substrateto which the pellicle is bonded, and to suppress residual stress due topellicle bonding, the shape of the agglutinant layer 14 is preferably aflat shape that is less likely to deform during bonding of the pellicle.

It was also found that more preferred results tended to be obtained whenthe agglutinant layer contained a polyvinyl ether compound.Specifically, when mixing was performed so that vinyl ether groups wereuniformly dispersed in the whole agglutinant layer, the peelingproperties of the agglutinant were further improved, and almost noresidues were observed in the visual inspection. Even when theagglutinant layer in which vinyl ether groups were uniformly dispersedwas bonded to a mask substrate and then irradiated with 193-nmultraviolet rays, dust was hardly generated, and the probability of goodpeeling substantially without leaving peeling residues on the masksubstrate was significantly increased.

That is, in the best mode of the present invention, the pellicle uses,as a base material that constitutes the mask agglutinant layer, anacrylic polymer having an SP value of 10.0 or more and 12.0 or less, andcontains a polyvinyl ether compound, whereby even when an exposure lightbeam is applied through the mask substrate, surface deterioration isreduced, and fine particulate residues are also reduced when thepellicle is peeled from the mask substrate. As a result, theregeneration cleaning of the mask substrate, from which the pellicle ispeeled, proceeds smoothly, the cleaning conditions can be loosened, andthere is an advantage in reducing damage to the mask surface duringcleaning.

Examples of the polyvinyl ether compound include homopolymers of vinylethers, such as methyl vinyl ether, ethyl vinyl ether, butyl vinylether, isobutyl vinyl ether, and (2-methoxyethyl) vinyl ether;copolymers of two or more vinyl ethers; copolymers of these vinyl ethersand other monomers; and the like. Among these, polyvinyl ether compoundscontaining methyl vinyl ether as a raw material monomer component arepreferable in terms of the control of peeling residues.

In the agglutinant that forms the agglutinant layer 14, the mixing ratioof an acrylic polymer mentioned above, and the polyvinyl ether compoundis, based on mass, 90:10 to 99:1, preferably 92:8 to 98:2, andparticularly preferably 94:6 to 96:4, in terms of reducing peelingresidues.

In addition, the agglutinant that forms the agglutinant layer of thepellicle may be mixed with other components, such as crosslinkingagents, tackifiers, plasticizers, stabilizers, viscosity regulators,antistatic agents, lubricants, conductivity-imparting agents, flameretardancy-imparting agents, thermal conductivity-improving agents, heatresistance-improving agents, weather resistance-improving agents,thixotropy-imparting agents, antioxidants, antimicrobial agents,antifungal agents, and coloring agents, depending on the purpose withinthe range in which the characteristics of the present invention are notimpaired.

As the means for forming the agglutinant layer 14, an uncured liquid orpaste agglutinant is applied to the lower end face of the pellicle frame11, followed by curing treatment, thereby forming an agglutinant layer.The agglutinant may be applied once, or may be repeatedly appliedseveral times in order to obtain a predetermined thickness of theagglutinant layer. In this case, the agglutinant is preferably allowedto stand between each time of coating until the shape of the agglutinantafter coating is stabilized. If it is difficult to apply an agglutinantdue to its high viscosity, the agglutinant may be applied, if necessary,after dilution with an organic solvent, alcohol, water, or the like toreduce the viscosity of the agglutinant. The agglutinant can be applied,for example, by dipping, spraying, or brush coating, or by using acoating device with a dispenser or the like. Coating using a coatingdevice with a dispenser is preferable, in terms of stability,workability, yield, and the like.

In the production of the pellicle 10, the coating and formation of theagglutinant layer 14 are generally performed first, followed bystretching of the pellicle film 12; however, the order may be reversed.For stretching the pellicle film 12, for example, an adhesive materialis applied to the upper end face of the pellicle frame 11, and thepellicle frame 11 is then heated to cure the adhesive material. Finally,the upper end face of the pellicle frame 11, on which the adhesivematerial layer 13 for bonding a pellicle film is formed, is bonded to apellicle film taken in an aluminum frame larger than the pellicle frame11, and extra portions of the pellicle film protruding outside thepellicle frame 11 are removed, thereby completing the pellicle.

Due to the use of the pellicle of the present invention with theconfiguration described above, the amount of agglutinant residues can bereduced when the pellicle is peeled from the exposure original plateafter being used in lithography. Moreover, the present inventionprovides a method for reducing peeling residues of the agglutinant layerof the pellicle by using the pellicle of the present invention.Therefore, the pellicle of the present invention is useful as a pelliclebonded to a phase shift photo mask having the delicate phase shift filmmentioned above, or a face comprising silicon oxide, such as quartz, asa main component.

The pellicle of the present invention is also useful as a pellicleapplied to exposure original plates whose agglutinant layer isirradiated with an exposure light beam during exposure, such as anegative type exposure original plate, an exposure original plate thathas a non-shaded area or a semi-transparent shaded area in a portionthereof to which an agglutinant is bonded, and an exposure originalplate that has a transparent area in a portion thereof to which anagglutinant is bonded. The agglutinant layer of the pellicle used insuch an exposure original plate is exposed to an exposure light beamthrough the exposure original plate from the face of the exposureoriginal plate opposite to the face provided with the pellicle.

The pellicle of the present invention may be used not only as aprotective member for suppressing the adhesion of foreign substances tothe exposure original plate in the exposure device, but also as aprotective member for protecting the exposure original plate duringstorage or transportation of the exposure original plate. An exposureoriginal plate with a pellicle can be produced by mounting the pellicledescribed above on an exposure original plate, such as a photo mask.

The method for producing a semiconductor device or a liquid crystaldisplay board according to the present embodiment comprises a step ofexposing a substrate (semiconductor wafer or liquid crystal originalplate) using the exposure original plate with a pellicle describedabove. For example, in the lithography step, which is one of the stepsfor producing semiconductor devices or liquid crystal display boards, inorder to form a photoresist pattern corresponding to an integratedcircuit etc. on a substrate, the exposure original plate with a pellicledescribed above is set on a stepper to perform exposure. As a result, ifforeign substances adhere to the pellicle in the lithography step, theforeign substances do not form images on the wafer coated with aphotoresist; thus, the short circuit, disconnection, and the like of theintegrated circuit etc. due to images of the foreign substances can beprevented. Therefore, the use of the exposure original plate with apellicle can improve the yield in the lithography step.

In general, when a desired number of times of lithography steps areperformed, when foreign substances and haze are generated, or when thepellicle film is damaged, the pellicle is peeled from the exposureoriginal plate, and the exposure original plate is subjected toregeneration cleaning in some cases. Due to the use of the pellicle ofthe present invention, peeling residues during repellicle can be reducedeven in the case of exposure original plates whose agglutinant layer isirradiated with an exposure light beam during exposure, such as anexposure original plate having a face comprising silicon oxide as a maincomponent in which peeling residues of the agglutinant layer are likelyto be generated, a negative type exposure original plate whoseagglutinant layer is irradiated with an exposure light beam more thanbefore, an exposure original plate that has a non-shaded area or asemi-transparent shaded area in a portion thereof to which anagglutinant is bonded, whose agglutinant layer is irradiated with anexposure light beam more than before, and an exposure original platethat has a transparent area in a portion thereof to which an agglutinantis bonded, whose agglutinant layer is irradiated with an exposure lightbeam more than before.

Moreover, since the use of the pellicle of the present invention canreduce peeling residues of the agglutinant layer, cleaning withfunctional water can be easily applied, and cleaning properties fordelicate exposure original plates, such as phase shift photo masks, canbe improved. In addition, the use of the pellicle of the presentinvention can contribute to the reduction of environmental burden causedby cleaning with functional water.

EXAMPLES

The present invention will be described in more detail below withreference to Examples. The “mask” in the Examples and ComparativeExamples is described as an example of the “exposure original plate.”Needless to say, it can also be applied to reticles.

Example 1

After a pellicle frame (external size: 149 mm×115 mm×3.5 mm, thickness:2 mm, flatness of an end face coated with a mask bonding agglutinant: 15um) made of an aluminum alloy was subjected to precision cleaning, anacrylic agglutinant manufactured by Soken Chemical Co., Ltd. (productname: SK-Dyne SN-70A, containing, as a base material, an acrylic polymerin which 95 mass % of monomer components was an ethylene oxidegroup-containing (meth)acrylate; SP value of the base material: 10.2)was applied to the end face with a flatness of 15 um, and allowed tostand for 60 minutes at room temperature. Thereafter, a separator wasplaced on an aluminum plate with a flatness of 5 um, and the pellicleframe coated with the agglutinant was placed so that the agglutinantfaced down. Thus, the agglutinant was brought into contact with the flatseparator and flattened.

Next, the pellicle on the aluminum plate was placed in an oven at 60° C.for 60 minutes to cure the agglutinant.

After the pellicle together with the aluminum plate was taken out fromthe oven, the separator was peeled.

Thereafter, an adhesive material manufactured by AGC Inc. (trade name:Cytop CTX-A) was applied to the end face opposite to the end face coatedwith the agglutinant. Then, the pellicle frame was heated at 130° C. tocure the adhesive material.

Finally, the adhesive material-coated end face of the pellicle frame wasbonded to a pellicle film taken in an aluminum flame larger than thepellicle frame, and portions outside the pellicle frame were removed,thereby completing the pellicle.

Next, a 6025 mask substrate (6 inch) and the previously preparedpellicle were set in a bonding device, and pressurized at a bonding loadof 50 N for a load time of 30 seconds to bond the pellicle to the masksubstrate.

After the mask substrate to which the pellicle was bonded was left for24 hours at room temperature, the back surface of the mask wasirradiated with ultraviolet rays at 10 mJ/cm² using a 193-nm ultravioletlamp so that the light beam was applied to the pellicle agglutinant.

After ultraviolet irradiation, the resultant was left for 1 hour at roomtemperature, and then the pellicle was slowly peeled upward from themask substrate at a speed of 0.1 mm/sec.

When the mask substrate after peeling was visually observed, a paleopaque band, which was considered to be agglutinant solute residues, wasslightly found in the contour portion to which the pellicle was bonded,and the surface of the mask substrate was obviously cleaner than theComparative Examples, described later. The residues could be removed bycleaning for 5 minutes in a cleaning tank using functional water(hydrogen and ammonia were added to ultrapure water) in combination withultrasonic waves (functional water overflowed).

Example 2

A pellicle was completed in the same manner using the same materials asin Example 1, except that the agglutinant used herein was an acrylicagglutinant manufactured by Soken Chemical Co., Ltd. (product name:SN-25B, containing, as a base material, an acrylic polymer in which 40mass % of monomer components was an ethylene oxide group-containing(meth)acrylate; SP value of the base material: 10.5). Further, thepellicle was bonded to and peeled from a mask substrate under the sameconditions as in Example 1.

When the mask substrate after peeling was visually observed, a paleopaque band, which was considered to be agglutinant solute residues, wasslightly found in the contour portion to which the pellicle was bonded,and the surface of the mask substrate was obviously cleaner than theComparative Examples, described later. The residues could be removed bycleaning for 5 minutes twice in a cleaning tank using functional water(hydrogen and ammonia were added to ultrapure water) in combination withultrasonic waves (functional water overflowed), as in Example 1.

Example 3

A pellicle was completed in the same manner using the same materials asin Example 1, except that the agglutinant used herein contained 3 massparts of a polyvinyl ether compound based on 100 mass parts of SK-DyneSN-70A. Further, the pellicle was bonded to and peeled from a masksubstrate under the same conditions as in Example 1.

When the mask substrate after peeling was visually observed, a paleshiny transparent band, which was considered to be agglutinant soluteresidues, was slightly found in the contour portion to which thepellicle was bonded, and the mask substrate was so clean that almost noagglutinant solute residue was confirmed. As for the subsequentcleaning, the residues could be removed by cleaning for 3 minutes usingthe same equipment as in Example 1.

Comparative Example 1

A pellicle was completed in the same manner using the same materials asin Example 1, except that the agglutinant used herein was an acrylicagglutinant manufactured by Soken Chemical Co., Ltd. (product name:SK-Dyne SK-1425S, containing, as a base material, an acrylic polymer notcontaining a (meth)acrylic acid ester having an ether bond as a monomercomponent; SP value of the base material: 9.8). Further, the pelliclewas bonded to and peeled from a mask substrate under the same conditionsas in Example 1.

When the mask substrate after peeling was visually observed, paleagglutinant solute residues were found in the portion to which thepellicle was bonded. The peeling residues could not be completelyremoved by cleaning for 5 minutes twice using the same equipment as inExample 1. Accordingly, light rubbing using a foamed polyvinyl alcoholwas necessary before cleaning.

Comparative Example 2

A pellicle was completed in the same manner using the same materials asin Example 1, except that the agglutinant used herein was an acrylicagglutinant manufactured by Soken Chemical Co., Ltd. (product name:SK-Dyne SK-1495S, containing, as a base material, an acrylic polymer notcontaining a (meth)acrylic acid ester having an ether bond as a monomercomponent; SP value of the base material: 9.2). Further, the pelliclewas bonded to and peeled from a mask substrate under the same conditionsas in Example 1.

When the mask substrate after peeling was visually observed, paleagglutinant solute residues were found in the portion to which thepellicle was bonded. The peeling residues could not be removed only byultrasonic cleaning with functional water, as in Comparative Example 1,but could be removed by the combined use of rubbing cleaning with afoamed polyvinyl alcohol before ultrasonic cleaning.

Synthesis Example 1

A 5-L flask equipped with a stirrer, a reflux condenser, a thermometer,and a gas inlet was charged with 320 g of butyl acrylate, 550 g of2-methoxyethyl acrylate, 80 g of acrylic acid, 50 g of 2-hydroxyethylacrylate, 1500 g of ethyl acetate, and 2 g of azobisisobutyronitrile asa polymerization initiator. Solution polymerization was carried out at68° C. for 8 hours in a nitrogen gas stream. After the completion of thereaction, 830 g of ethyl acetate was added thereto, thereby obtaining asolution of an acrylic polymer with a solid content of 30% (SP value:10.6). A polyisocyanate solution was added to the obtained acrylicpolymer solution, and the mixture was stirred and mixed to obtain anagglutinant.

Synthesis Example 2

A 5-L flask equipped with a stirrer, a reflux condenser, a thermometer,and a gas inlet was charged with 400 g of 2-ethylhexyl acrylate, 500 gof 2-ethoxyethyl acrylate, 100 g of acrylic acid, 1200 g of ethylacetate, and 2 g of azobisisobutyronitrile as a polymerizationinitiator. Solution polymerization was carried out at 68° C. for 8 hoursin a nitrogen gas stream. After the completion of the reaction, 1130 gof ethyl acetate was added thereto, thereby obtaining a solution of anacrylic polymer with a solid content of 30% (SP value: 10.1). Apolyisocyanate solution was added to the obtained acrylic polymersolution, and the mixture was stirred and mixed to obtain anagglutinant.

Synthesis Example 3

A 5-L flask equipped with a stirrer, a reflux condenser, a thermometer,and a gas inlet was charged with 350 g of 2-ethylhexyl acrylate, 550 gof 2-methoxyethyl acrylate, 50 g of methacrylic acid, 50 g of2-hydroxyethyl methacrylate, 1400 g of ethyl acetate, and 2 g ofazobisisobutyronitrile as a polymerization initiator. Solutionpolymerization was carried out at 68° C. for 8 hours in a nitrogen gasstream. After the completion of the reaction, 930 g of ethyl acetate wasadded thereto, thereby obtaining a solution of an acrylic polymer with asolid content of 30% (SP value: 10.2). A polyisocyanate solution wasadded to the obtained acrylic polymer solution, and the mixture wasstirred and mixed to obtain an agglutinant.

Synthesis Example 4

A 5-L flask equipped with a stirrer, a reflux condenser, a thermometer,and a gas inlet was charged with 300 g of butyl acrylate, 550 g of2-methoxyethyl acrylate, 100 g of 2-hydroxybutyl acrylate, 50 g ofitaconic acid, 1500 g of ethyl acetate, and 2 g ofazobisisobutyronitrile as a polymerization initiator. Solutionpolymerization was carried out at 68° C. for 8 hours in a nitrogen gasstream. After the completion of the reaction, 830 g of ethyl acetate wasadded thereto, thereby obtaining a solution of an acrylic polymer with asolid content of 30% (SP value: about 10.7). A polyisocyanate solutionwas added to the obtained acrylic polymer solution, and the mixture wasstirred and mixed to obtain an agglutinant.

Synthesis Example 5

A 5-L flask equipped with a stirrer, a reflux condenser, a thermometer,and a gas inlet was charged with 300 g of butyl acrylate, 600 g ofmethoxypolyethylene glycol acrylate, 100 g of acrylic acid, 1400 g ofethyl acetate, and 2 g of azobisisobutyronitrile as a polymerizationinitiator. Solution polymerization was carried out at 68° C. for 8 hoursin a nitrogen gas stream. After the completion of the reaction, 930 g ofethyl acetate was added thereto, thereby obtaining a solution of anacrylic polymer with a solid content of 30% (SP value: about 10). Apolyisocyanate solution was added to the obtained acrylic polymersolution, and the mixture was stirred and mixed to obtain anagglutinant.

Examples 4 to 8

Pellicles were produced in the same manner as in Example 1, except thatthe agglutinant used herein was each of the agglutinants obtained inSynthesis Examples 1 to 5, and a peeling test was performed. As aresult, the pellicles using any of the agglutinants resulted in reducedpeeling residues and had improved cleaning removing properties, comparedwith the Comparative Examples.

EXPLANATION FOR REFERENCE NUMERALS

-   1: exposure original plate-   10: pellicle-   11: pellicle frame-   12: pellicle film-   13: adhesive material layer for bonding pellicle film-   14: agglutinant layer-   15: air pressure adjustment hole (vent)-   16: dust removal filter

1. An agglutinant for pellicles for bonding a pellicle to an exposureoriginal plate, the agglutinant comprising an acrylic polymer having anSP value of 10.0 or more and 12.0 or less as a base material.
 2. Anagglutinant for pellicles for bonding a pellicle to an exposure originalplate, the agglutinant comprising an acrylic polymer as a base material,the acrylic polymer comprising a (meth)acrylic acid ester having anether bond as a monomer component.
 3. An agglutinant for pellicles asclaimed in claim 2, wherein the (meth)acrylic acid ester having an etherbond is a (meth)acrylic acid ester having an alkylene oxide group.
 4. Anagglutinant for pellicles as claimed in claim 3, wherein the(meth)acrylic acid ester having an ether bond is contained in an amountof 30 mass % or more based on the whole monomer components.
 5. Anagglutinant for pellicles as claimed in claim 3, wherein the alkyleneoxide group is an ethylene oxide group.
 6. An agglutinant for pelliclesas claimed in claim 2, further comprising an unsaturated monomer havinga carboxyl group or a hydroxyl group as a monomer component.
 7. Anagglutinant for pellicles as claimed in claim 2, further comprising a(meth)acrylic acid alkyl ester as a monomer component.
 8. An agglutinantfor pellicles for bonding a pellicle to an exposure original plate, theagglutinant comprising an acrylic polymer as a base material, theacrylic polymer having a side chain containing an ether bond.
 9. Anagglutinant for pellicles as claimed in claim 8, wherein the side chaincontaining an ether bond has an alkylene oxide group.
 10. An agglutinantfor pellicles as claimed in claim 9, wherein the alkylene oxide group isan ethylene oxide group.
 11. An agglutinant for pellicles for bonding apellicle to an exposure original plate, the agglutinant comprising anacrylic polymer as a base material, the acrylic polymer having a sidechain that has higher degradability by irradiation with an exposurelight beam than a main chain.
 12. An agglutinant for pellicles forbonding a pellicle to an exposure original plate, the agglutinantcomprising an acrylic polymer as a base material, the acrylic polymerhaving a side chain that is selectively degraded by irradiation with anexposure light beam.
 13. A pellicle frame with an agglutinant layer,comprising a pellicle frame and an agglutinant layer provided on one endface of the pellicle frame and obtained from an agglutinant forpellicles as claimed in claim
 1. 14. A pellicle comprising a pelliclefilm, a pellicle frame provided with the pellicle film on one end facethereof, and an agglutinant layer provided on the other end face of thepellicle frame and obtained from an agglutinant for pellicles as claimedin claim
 1. 15. A pellicle as claimed in claim 14, wherein theagglutinant layer is irradiated with an exposure light beam.
 16. Apellicle as claimed in claim 14, wherein the pellicle is bonded to aphase shift photo mask.
 17. A pellicle as claimed in claim 14, whereinthe pellicle is bonded to a negative type exposure original plate.
 18. Apellicle as claimed in claim 14, wherein the pellicle is bonded to anexposure original plate that has a non-shaded area or a semi-transparentshaded area in a portion thereof to which an agglutinant layer isbonded.
 19. A pellicle as claimed in claim 14, wherein the pellicle isbonded to an exposure original plate that has a transparent area in aportion thereof to which an agglutinant layer is bonded.
 20. A pellicleas claimed in claim 14, wherein the pellicle is bonded to a facecomprising silicon oxide as a main component.
 21. A pellicle as claimedin claim 20, wherein the face comprising silicon oxide as a maincomponent is a quartz face.
 22. A pellicle as claimed in claim 14,wherein the pellicle is compatible with regeneration cleaning withfunctional water.
 23. An exposure original plate with a pellicle,comprising an exposure original plate and a pellicle as claimed in claim14 mounted on the exposure original plate.
 24. An exposure originalplate with a pellicle as claimed in claim 23, wherein the exposureoriginal plate is a phase shift photo mask.
 25. An exposure originalplate with a pellicle as claimed in claim 23, wherein the exposureoriginal plate is of negative type.
 26. An exposure original plate witha pellicle as claimed in claim 23, wherein a portion of the exposureoriginal plate to which the agglutinant layer is bonded has a non-shadedarea or a semi-transparent shaded area.
 27. An exposure original platewith a pellicle as claimed in claim 23, wherein a portion of theexposure original plate to which the agglutinant layer is bonded has atransparent area.
 28. An exposure original plate with a pellicle asclaimed in claim 23, wherein the exposure original plate comprisessilicon oxide as a main component.
 29. An exposure original plate with apellicle as claimed in claim 23, wherein the exposure original plate isa quartz substrate.
 30. A method for producing a semiconductor device,comprising a step of performing exposure using an exposure originalplate with a pellicle as claimed in claim
 23. 31. A method for producinga liquid crystal display board, comprising a step of performing exposureusing an exposure original plate with a pellicle as claimed in claim 23.32. A method for regenerating an exposure original plate, comprisingpeeling a pellicle from an exposure original plate with a pellicle asclaimed in claim 23, and cleaning residues of an agglutinant remainingon the exposure original plate with functional water to regenerate theexposure original plate.
 33. A peeling residue reduction methodcomprising, when peeling a pellicle from an exposure original plate towhich the pellicle is bonded, reducing peeling residues of anagglutinant layer of the pellicle remaining on the exposure originalplate, wherein the method uses a pellicle as claimed in claim 14 as thepellicle.